Telomerization with sulfuryl halide and product thereof



United States Patent 'TELOMERIZATION WITH SULFURYL HALIDE AND PRODUCT THEREOF William S. Barnhart, Cranford, N. 1., assignor to The M. W. Kellogg Company, Jersey City, N. J., a corporation of Delaware No Drawing. Application June 19, 1952, Serial No. 294,495

20 Claims. (Cl. 260-653) This invention relates to low molecular weight, halogen-containing telomers and their preparation. In one aspect, this invention relates to a method of preparing liquid, grease and wax-like halotelomers containing halogen terminal groups, preferably chlorine.

Liquid, grease and wax-like telomers of fluoroethylenic and chlorofluoroethylenic compounds may be used in such capacities as plasticizers, rubber softeners, nonflammable hydraulic fluids, 'heat transfer media, lubricants, dielectric fluids and potting compounds.

For the purpose of this invention the term telomer means both homotelomers and cotelomers. The term homotelomer refers to those telomeric materials containing the same monomer units. The term cotelomers refers to those telomeric materials containing monomer units of two or more diiferent monomers. The terms polymerization or telomerization in their broadest sense include both homopolymerization and copolymerization, and 'homotelomerization and cotelomerization, respectively.

Homotelomeric haloethylenic materials of an oil, grease or wax-like nature, but of different composition than those disclosed in this invention, have been prepared by telomerizing the haloethylenic monomer in the presence of telogens, such as chloroform and carbon tetrachloride, in mol ratios of about 9:1 with the monomer. By this prior art practice some liquid and oily telomeric materials have been obtained, but the major product of the telo- .merization is of a high molecular weight, non-distillable wax-like nature, which requires pyrolyzing to yield liquids, oils, or greases. These telomeric products of halogen substituted ethylene contain an odd number of carbon .atoms as illustrated by the following formula:

wherein A is chlorine or hydrogen and X is a haloethylenic monomer unit. The pyrolysis of these telomers must be carried out at extremely high temperatures and in a vacuum system to obtain a maximum yield of low molec- 2,770,659 Patented Nov. 13, 1956 ular weight products. The major product of the pyrolysis is the gaseous monomer itself. Only 10 percent to 40 percent of the total yield of the pyrolysis is composed of the liquid, oil, grease and soft wax-like products. These products are unsaturated and therefore chemically unstable. To render the pyrolyzed fiuoroethylenic and chlorofiuoroethylenic products resistant to heat, light and chemical attack, fluorination of the unstable products with expensive reagents, such as cobalt trifluoride or chlorine trifluoride, is required.

Attempts, by the use of several chlorine donating compounds, to prepare telomers containing halogen terminal groups as set forth in this invention, have led to assorted products. For example, when chlorine was used as a telogen, only chlorination of the monomer resulted indicating that the chlorination took place at a speed in excess of the speed of the polymerization action. On the other hand with hydrochloric acid, the products obtained were primarily high molecular weight solids containing hydrogen terminal groups. Thionyl chloride yielded high molecular weight solids containing a chlorine and also a SOCl terminal group.

An object of the present invention is to provide distillable liquid or 'oil, grease and wax-like telomeric materials containing halogen terminal groups and a convenient and efficient method for making same.

Another object of this invention is to provide a method for preparing distillable liquid or oil, grease and waxlike perfluoroethylenic and perchloroiluo-roethylenic telomeric materials containing chlorine terminal groups, which require no further fluorination to render them stable to heat, light or chemical attack.

Another object of this invention is to provide a method for preparing distillable liquid, grease and wax-like telomeric materials by a one step process, the products of which may be separated and purified by convenient and conventional methods.

Still another object of this invention is to provide a method for preparing distillable and stable liquid, grease and wax-like telomeric materials which, without separation or further treatment, exhibit superior plasticizing properties.

Another object of this invention is to provide a method for preparing distillable liquid, oil, grease and wax-like telomeric materials in high yield based upon the monomer charged.

Still another object of this invention is to provide homotelomers and cotelomers which contain an even number of carbon atoms.

Various other objects and advantages will become apparent to thoseskilled in the art from the accompanying description and disclosure.

The above objects are accomplished according to this invention by directly telomerizing haloolefinic monomer or monomers with a catalyst and in the presence of a sulfuryl halide as the telogen, to produce a substantially saturated telomer. The telogen, namely the sulfuryl halide, provides halogen terminal groups, tends to control telomerization and terminates free radical reactions so that by varying the amount of telogen used, the telomeric material may be obtained primarily as a liquid or oil, a grease or a soft wax, which is recovered as the product of the process.

The compounds formed by telomerization in the presence of a sulfuryl halide have the general formulae:

wherein W is a member selected from the group consisting of fluorine, chlorine and bromine, X is a haloolefinic, preferably haloethylenic, monomer unit and n is an integral greater than one, preferably at least 4 and preferably not more than 20, and

wherein W is a member selected from the group consisting of fluorine, chlorine and bromine, X and Y are different haloolefinic, preferably ethylenic, monomer units and n and m are integrals and preferably each is greater than one, and each is not greater than 10.

The reaction occurs essentially as shown below in a typical reaction using chlorotrifluoroethylene and sulfuryl chloride as an example:

As shown, sulfur dioxide gas is formed as well as a clear polymeric mass, usually in gel-like form, which includes various grades of telomeric halocarbons, such as liquids, oils, greases and soft Waxes. These telomeric haloc-arbons may be separated by conventional distillation. The distillable substances obtained by telomerizing chlorotrifluoroethylenic compounds in the presence of sulfuryl chloride are sufliciently stable as not to absorb apprech able amount of fluorine even though exposed to the gas for 24 hours at a temperature of 60 C. or to significantly pyrolyticly decompose at temperatures up to 200 C.

The halogen atoms of the sulfuryl halides are selected from the group consisting of fluorine, chlorine and bromine, and mixtures thereof. The preferred telogen, sulfuryl chloride, is usually prepared by the catalytic combination of sulfur dioxide and chlorine gas. Other sulfuryl halides useful in the present invention include SOzFz, SOzBrz, SOzFCl, and SOzBrCl. It is also within the scope of this invention to generate the sulfuryl halide in situ, i. e., by passing into the telomerizing mass a mixture of S02 and halogen, in the proper stoichiometric quantities, either as liquids or gases or both.

Generally accepted among those skilled in the art is the concept that compounds which homopolymerize or homotelomerize are those that contain =Cl 2 and/or :CFs groups. It is also Well-known that compounds which will not readily homopolymerize or homotelomerize may be copolymerized or cotelomerized with other monomers. The haloolefinic compounds which may be used as starting monomers in the present invention are any polymerizahle compounds containing double bond between two carbon atoms and at least one halogen atom attached to at least one of the carbon atoms attached to the double bond. The halogen attached to the carbon of the double bond may be fluorine, chlorine, bromine or iodine. Experimental evidence has shown that compounds containing a halogen attached to one of the carbon atoms attached to the double bond is sufficiently stable to halogenation that it may be successfully telomerized according to the teachings of this invention. Styrene and acrylonitrile, on the other hand, when subjected to similar conditions yielded the chlorinated monomers.

The present invention is particularly applicable to the telomerization of perfluorochloro olefins, such as chlorotrifluoroethylene, perfluoro olcfins, such as tetrafiuoroethylene, chloro olefins, such as vinyl chloride, and fluoro olefins, such as vinylidene fluoride. The invention contemplates the telomerization of various polymerizable halogenated olefins; for example, perfluorobutadiene, a-methyl phenyldifluoroethylene, difluorodichloroethylone, pertluoroacrylonitrile, perfluorostyrene, perfluorocyclobutenc, a-chlorostyrene, 2-chloropropene, vinylidene chloride, vinyl bromide, tetrachloropropene, chlorobutadiene, a-bromostyrene, bromotrifluoroethylene, unsym. dibromodifluoroethylene, trifluoroethylene, vinyl fluoride, etc. As previously mentioned, the present invention applies to the cotelomerization of these monomers, as well as their homotelomerization. For example, the invention applies to the cotelomerization of chlorotrifluoroethylene and tetrafluoroethylene. In the cotelomeriz-ation, the second monomer or comonomer is a halogenated olefin, and preferably an olefin in which the halogen is selected from a group consisting of fluorine and chlorine. The monomers may also be cotelomerized with a wide range of compounds which do not readily homopolymerize or homotelomerize. For example, the invention contemplates the cotelomerization of compounds of the nature of sym. dichlorodifluoroethylene and trichloroethylene incorporated with such compounds as chlorotrifluoroethylone and tetrafluoroethylene.

It is also within the scope of this invention that unsaturated bonds which may exist in the product after the telomeric chains have been formed may be halogenated by the telogen. This is to be expected when diolefins, such as perfluorobutadiene, are used as starting materials. it is also within the scope of this invention that a halogen, such as iodine, of the monomer unit may be replaced with another halogen donated by the telogen.

The present invention is not limited to use in any one particular type system or apparatus. In one aspect the telomerization may be carried out by means of a batch process which comprises telomerizing the monomer in the presence of a catalyst, a sulfuryl halide, and an inert solvent, if desired, under autogenous pressure.

More particularly, a system designed to withstand moderate pressures, which are autogeneous during the telomerization, is flushed out with nitrogen to remove any oxygen and subsequently charged with the catalyst, preferably benzoyl peroxide, a telogen, preferably sulfuryl chloride, and a solvent, if desired. The system is closed and the haloethylenic monomer, or monomers, is added as a gas under pressure or as a liquid at low temperatures. The mixture is then heated to a temperature between about 0 C. and about 200 C. and preferably between about 25 C. and about C. During the telomerization some type of agitation is preferable but not essential. As the telomerization proceeds, a maximum pressure is oon reached which subsequently slowly subsides. When the pressure ceases to drop, the heat is discontinued and the gaseous materials, such as unreacted monomer, which may be present are bled from the autoclave. These may, if desired, be fractionated to separate and recover free sulfur dioxide and unrcacted monomer. The product of the telomerization is stripped of the excess sulfuryl chloride, solvent and chlorinated monomer, by heating. Acidic impurities .are then removed from the remaining telomeric material but such methods as treatment with silica gel, alumina, activated carbon or washing it with aqueous ammonia or alkali. The product may then vbe distilled if individual fractions are desired.

In another embodiment of the invention, the telomerization may be carried out by means of a continuous process comprising feeding the reactants into a reaction Zone at a rate determined to maintain consistent proportions of the constituents in the mixture and to produce a residence time of about /2 hour to 24 hours, preferably 1 to 6 hours. The apparatus may be modified so that each ingredient is added individually, or the catalyst may be dissolved in the sulfuryl chloride, or each may be dissolved in a suitable solvent, or the catalyst and the sulfuryl chloride exist in the same solution.

More particularly in a continuous system, reagent tanks for the catalyst, sulfuryl chloride and the monomer, pipe coil reactor in a heating bath and a cooling coil leading to a product storage tank are used. Nitrogen pressure may be applied to the reagent tanks or to the unit as desired.

Yields, usually above 70 percent and frequently above 90 percent based upon the weight of monomer charged, of chlorotrifluoroethylene homotelomers and tetrafluoroethylene homotelomers have been prepared by the operation of the above procedure.

The mol ratio of sulfuryl chloride to monomer employed in these procedures is between about 2:1 and about 1:10, preferably between 1:1 and 1:4 depending upon the products desired and the starting materials used. The optimum mol ratio, for producing primarily telomeric chlorotrifluoroethylene oils and greases, is 1:2 of the telogen to monomer. The telomerization may be carried out in the presence of a suitable inert solvent, if desired. The term inert solvent means any liquid which does not materially alter the normal telomerization of haloethylenic compounds in the presence of sulfuryl chloride; such as Freon 113, tetrachloroethylene or tetrachloroethane. It should be noted that water slowly reacts with sulfuryl chloride to form hydrochloric acid and sulfric acid and therefore precautions should be taken to provide substantially anhydrous conditions. Glass lined equipment is usually desirable, however Monel and stainless steel have been used for polymerization and filtration apparatus without noticeable corrosion.

Polymerization catalysts which are not destroyed by halogenation at temperatures within the operating range and which are soluble in one or more of the constituents of the telomerization mixture may be used in the prac tice of this invention. For example, the telomerization may be carried out by catalysis with aromatic peroxides, such as benzoyl peroxide, chlorinated aromatic peroxides, such as dichlorobenzoyl peroxide, aliphatic peroxides,

such as di-t-butyl peroxide, chlorinated aliphatic peroxides,

such as trichloroacetyl peroxide, metal compounds, such 1 as tetraethyl lead, gases, such as oxygen, and sunlight.

l-laloethylenic telomers, telomerized with SO2Cl2, contain only negligible amounts of sulfur, generally less than 0.1 percent. In the case of chlorotrifluoroethylene telomers, the four-carbon and six-carbon compounds have been isolated from sulfuryl chloride modified oil and the end carbon groups of these compounds have been identitied as -CF2C1 and -CFC12. The four-carbon compound has a boiling point of 137 C., N of 1.380, 414 of 1.72 and M. R. (observed) of 41.0 versus a calculated 40.1 for CaCliFs. The six-carbon has a boiling point of 207 C., N of 1.385, 114. of 1.82 and M. R. (observed) of 54.3 versus a calculated 52.2 for CsClsFs.

Although liquid, oily and greasy homotelomers of chlorotrifluoroethylene and cotelomers of chlorotrifluoroethylene and tetrafluoroethylene may readily be prepared by telomerizingin the presence of sulfuryl chloride, telomers of tetrafiuoroethylene appear primarily in a soft wax-like condition. It should be borne in mind that telomers of tetrafluoroethylene containing as few as five monomer units are solids or waxes at room temperature. The homotelomers of tetrafluoroethylene are, however, compatible with both chlorotrifiuoroethylene polymers and polytetrafluoroethylene molding powder. Cotelomers of chlorotrifluoroethylene and tetrafluoroethylene range in state from liquids to solids, depending upon the mol ratio of the monomers and upon the amount of telogen, preferably sulfuryl chloride, employed during the telomerization. Cotelorners of these compounds containing 10 percent chlorotrifluoroethylene and 90 percent tetrafluoroethylene are liquids and oils, while cotelomers containing 1 percent chlorotrifiuoroethylene and 99 percent tetrafiuoroethylene are soft wax-like solids.

Liquid homotelomers of 1,1-dichloro-2,2-difluoroethylene and liquid and solid telomers of vinyl chloride have also been obtained by telomerization in the presence of sulfuryl chloride.

telomers have successfully been used as plasticizers in plastics derived from similar starting materials. Until recently, these plasticizers consisted of a fraction of the total polymeric mass, which contained assorted low molecular weight polymeric materials boiling within a tem perature range of about 50 C. An improved plasticizer was obtained when the components of the plasticizer were not limited to those materials boiling within such a restricted temperature range, but included all of the polymeric materials above 200 C. at 760 mm. and in such proportions that the average molecular weight lay between 200 and 2000. Uncracked polymeric material telomerized with carbon tetrachloride or chloroform in mol ratios as high as :1 with the monomer, exhibit average molecular weights in excess of the optimum range and the total material boiling above 200 C. cannot be used as plasticizer until cracked and stabilized.

The chlorotrifluoroethylenic plastic containing 25 per cent of the SO2Cl2 modified plasticizer is transparent, does not exude plasticizer after one week and does not whiten when severally folded or flexed. The plasticizer has been found to be as efiicient as other plasticizers at room temperature and more eflicient at low temperatures. It is also less volatile and more compatible with the plastic than plasticizers prepared by other methods.

To facilitate a fuller and more complete understanding of the subject matter in this invention and how the herein described invented compounds can be prepared by practice of the invented process, certain specific examples herewith follow, but it is to be understood that these examples are provided by way of illustration and should not be considered unnecessarily limiting to the invention.

Wherever the term parts is used, it is intended to mean parts by weight.

EXAMPLE 1.TELOMERIZATION OF CHLOROTRIFLUOROETHYLENE The pressure system was flushed out with nitrogen and charged with a peroxide solution (3.5 parts of benzoyl peroxide dissolved in 308 parts of carbon tetrachloride) and parts of sulfuryl chloride. The system was cooled to about -25 C. or lower and 116 parts of chlorotrifluoroethylene monomer was added. The system was closed and heated to about 95 C. for a period of four hours during which time the mixture was mechanically agitated. A maximum gage pressure of 300 pounds per square inch was reached and then gradually subsided. At the end of the telomerization the gases were bled from the system and the liquid product was transferred to a distilling pot. The excess sulfuryl chloride and carbon tetrachloride (solvent) were boiled off by heating the mixture to a pot temperature of C. at atmospheric pres sure. The gel-like product was distilled at a vapor temperature up to C. at 35 mm. of mercury to remove very low molecular weight polymers. Final distillation was conducted at 0.5 mm. pressure and at a vapor temperature up to about 230 C. The telomerization yield was 78 percent with 93 percent of the product distilled.

EXAMPLE 2.TELOMER1ZAT1ON OF OHLOROTRIFLUOROETHYLENE 5.3 parts of benzoyl peroxide containing 10 percent water were dissolved in 50 parts of Freon 113. The solu tion was filtered to remove water. After flushing the polymerization system with nitrogen, the peroxide solution and 135 parts of sulfuryl chloride and 350 parts of chlorotrifluoroethylene were charged into the pressure vessel. Telomerization was conducted for four hours at a, temperature of 100 C. At the end of the telomenization, the gases recovered from the pressure system were found. to contain 11 parts of unreacted monomer and 25 parts of sulfur dioxide. Distillation of the liquid product at a, temperature of about 100 C. yielded 75 parts Freon 113 and 43 parts unreacted sulfuryl chloride. The remaining EXAMPLE 3.TELOMER IZATION OF TETRAFLUOROETHYLENE A silver lined bomb was flushed out with nitrogen, cooled to about C. and charged with 57 parts of sulfuryl chloride and .844 part benzoyl peroxide. The system was then closed and 42.2 parts of tetrafiuoroethylene were charged under pressure into the reactor. The mixture was heated to a temperature of 95 C. and the gage pressure soon reached a maximum of 500 pounds per square inch which subsided to 250 pounds per square inch during a period of one hour. The low boiling constituents of the telomerization product were stripped off by opening the system and heating the mixture to a temperature of about 8 EXAMPLE 5.TELOMERIZATION OF 1,1DI-. CHLORO-2,Z DIFLUOROETHYLENE 45.6 parts of 1,1-dichloro-2,Z-difluoroethylene were telomerized with 49.6 parts of sulfuryl chloride and 4.72 parts of benzoyl peroxide at 100 C., by the method described above. Upon distillation, a liquid fraction (B. P. C. to 100 C. at 0.1 mm.) and a residue were obtained.

EXAMPLE 6.TELOMER'IZATION OF VINYL CHLORIDE A pressure system was flushed with nitrogen and charged with 0.72 part benZoyl peroxide and 80.3 parts of sulfuryl chloride. The system was then cooled and 18 parts of vinyl chloride were added. The system was closed, allowed to reach room temperature and agitated for 4 hours. The products recovered consisted of liquid and low molecular weight solid telomers.

EXAMPLE 7.-VAR1ABLES IN CHLOROTRI- FLUOROETHYLENE TELOMERIZATION The variables involved in the telomerization of chlorotrifluoroethylene with sulfuryl chloride are illustrated by the following Table I:

Table l VARIABLES INVOLVED IN THE TELOMERIZATION OF CHLOROTRIFLUOROETHYLENE Eliect of Solvent Efiect of Modifier Efieet of Catalyst Sample N0 B-51A 13-51B B-51G B-52A B-52B B-52C B-53A 13-5313 B-53C TFOE, mols 3 3 3 3 3 3 3 3 3 SOzOlz, 111015-- 1. 5 1. 5 1. 5 1. 0 1. 5 2. 0 1. 5 1. 5 1. 5 0014, 111015.... 0 1. 0 2. 0 0. 5 0. 5 0. 5 0. 5 0. 5 0. 5 E2102, mols 03 03 03 03 03 03 015 03 06 Yield, percent 76 77 71 79 91 61 79 88 Boiling Point of Fraction at Atmospheric Pressure (extrapolated):

below 300 0. percent comp 30. 8 27. 0 29. 3 16. 6 32. 0 34. 4 23. 3 28. 5 34. 0

below 350 0. percent comp... 12. 6 6.0 4.0 10. 3 11.4 8. 1 5. 5 13. 5 9. 1

below 400 C. percent c0mp 13. 1 14. 5 5. 2 7. 5 10.7 11.9 13. 5 8. 9 10. 1

below 450 0. percent comp... 11. 1 11. 5 8. 2 9. 6 11. 8 11.3 12. 7 12.6 11.8

below 500 0. percent comp. 13.1 10.4 18.0 8.8 8.0 8. 5 12.5 12.0 8.8

below 550 0. percent comp 6. 8 10.6 7. 3 8. 5 9. 8 12.6 9.4 4. 5 6. 4

above 550 C. percent comp 12.5 20. 0 27.0 38. 7 16. 3 13. 2 23. 1 20.0 19. 8

1 Based on monomer charged.

EXAMPLE 4.COTELOMERIZATION OF CHLORO- TRIFLUOROETHYLENE AND TETRA FLUORO- ETHYLENE The pressure system was flushed with nitrogen, cooled to 30 C. and charged with 1.1 parts benzoyl peroxide, 49.5 parts sulfuryl chloride and 32.2 parts chlorotrifluoroethylene. The system was closed and 18.35 parts of tetrafluoroet-hylene were charged under pressure into the reactor. The mixture was then heated to a temperature of 95 C. and a maximum gage pressure of 450 pounds per square inch was reached. The product of the telomerization was treated with silica gel and distilled to yield 21.1 parts of liquid cotelomer.

EXAMPLE 8.PREPARATION OF CHLOROTRI- FLUOROETHYLENE PLASTICIZER This example illustrates the preparation of chlorotrifluoroethylene plasticizer. 57 parts of monomer were telomerized with 41.3 parts of sulfuryl chloride and 1.77 parts of benzoyl peroxide. The product was stripped of low molecular weight components by heating the mixture to a temperature of about C., 51 parts (90 percent yield based on monomer charged) of undistilled product remained. The sample was then heated with 10 weight percent silica, filtered and then stripped again at a temperature of about C. at 20 mm. pressure to give a 62 percent yield of undistilled mixed plasticizer containing the usual pot residue.

EXAMPLE 9.OHLOROTRIFLUOROETHYLENE PLASTICIZER The following Table II compares the relative effectiveness of the various firactions of chlorotrifluoroethylene telomers when used as plasticizers for polymeric chlorotrifluoroethylenic plastics:

Table II PLASTICIZING EFFICIENCY OF CHLOROTRIFLUOROETHYLENE OIL FRACTIONS [Composition containing percent plasticizer and 75 percent chlorotrifiuoroethylene plastic] I. These measurements Were made upon the original polymeric chlorotritluoroethylene plastic which contained no plasticizer of any kind.

II. These measurements were made upon the polymeric chlorotrifluoroethylenic plastic which contained a plasticizer consisting of low molecular weight chlorotrifluoroethylenic polymers with extrapolated boiling points of 350 C. to 450 C. at atmospheric pressure (actual measurement 130 C. to 200 C. at 0.5 mm), wh1ch were prepared by pyrolyzing higher molecular weight polymers.

Q III. These measurements were made upon the polymeric chlorotr fluoroethylene plastic which contained a plasticizcr consisting of low molecular weight chlorotrlfluoroethylene telomers with extrapolated boiling points of 350 C. to 450 C. at atmospheric pressure (actual measurement 130 C. to 200 C. at 0.5 mm.), which were prepared by telomerizing c111orotrifiuoroethylene monomer with sulfuryl chloride.

IV. These measurements were made upon the polymeric chlorotrifluoroethylene plastic which contained a plasticizer consisting of chlorotrifiuoroethylene telomers with extrapolated boiling points 300 C. to 550 C. at atmospheric pressure (actual measurement 95 C. to 270 C. at 0.5 mm), which were prepared by telomerizmg chlorotrifluoroethylene monomer with sulfuryl chloride.

V. These measurements were made upon the polymeric chlorotrifiuoroethylenc plastic which contained a plasticizer consisting of telomeric chlorotrifiuoroethylene from which only the light polymer ends boiling below the extrapolated boiling point 300 C. at atmospheric pressure (actual measurement 95 C. at .5 mm.) were stripped.

VI. These measurements were made upon the polymeric chlorotrifluoroethylene plastic which contained a plasticizer consisting of telomeric chlorotrifluoroethylene with extrapolated boiling points above 550 C. at atmospheric pressure (actual measurement 270 C. at .5 mm).

It is to be understood that various modifications and alterations of conditions and technique obvious to those skilled in the art may be made in this invention without departing from the scope thereof. To a large extent the conditions of telomerization will depend upon the olefin being telomcrized and upon the technique used. For example, with pcrfluoroethylcncs and perfluorochlorocthylenes temperatures between about 80 C. and about 125 C. are most satisfactory. In a continuous system some what lower residence times are employed than in batch type systems because lower yields are permissible with recycle of unrcacted monomer. In autogcnous batch type systems the residence time is about 2 to about 5 hours, but this depends to a large extent upon the monomer used, and may be as short as 10 minutes without departing from the scope of this invention.

Having described my invention, I claim:

1. A process for the production of a distillable open chain compound having a general formula selected from the group consisting of in which X is a haloolcfin and Y is a different haloolefin, W is a halogen selected from the group consisting of fluorine, chlorine and bromine and n and m are integers at least one being greater than 1 which comp-rises reacting a polymerizablc compound containing a double bond between two carbon atoms and at least one halogen atom attached to at least one of the carbon atoms of the double bond under liquid phase and substantially anhydrous conditions in the presence of a sulfuryl halide such that the sulfuryl halide provides halogen terminal groups and sulfur dioxide is released, the halides being selected from at least one of the group consisting of fluorine, chlorine and bromine.

2. The process of claim 1 in which said sulfuryl halide is sulfuryl chloride.

3. The process of claim 1 in which said sulfuryl halide is sulfuryl fluorochloride.

4. The process of claim 1 in which said sulfuryl halide is sulfuryl bromochlon'de.

5. The product of the process of claim 1.

6. A process for the production of a distilla-ble open chain compound having a general formula selected from 5 the group consisting of in which X is a haloolefin and Y is a different haloolefin, W is a halogen selected from the group consisting of fluorine, chlorine and bromine and n and m are integers at least one being greater than 1 which comprises reacting a polymerizable compound containing a double bond between two carbon atoms and at least one halogen atom attached to at least one of the carbon atoms of the double bond at a temperature between about 0 C. and about 200 C. for a period of time between about one-half hour and about 24 hours under liquid phase and anhydrous conditions with a catalyst effective under the conditions of reaction to promote the reaction and in the presence of a sulfuryl halide such that the sulfuryl halide provides halogen terminal groups and sulfur dioxide is released, the halides being selected from at least one of the group consisting of fluorine, chlorine and bromine.

7. The process of claim 6 in which the mol ratio of su-rfuryl halide to monomer is between about 1 to 10 and about 2 to 1.

8. The process of claim 6 in which said polymerizablc compound is vinyl chloride.

9. A process for the production of a distillable open chain compound having the general formula in which X is a haloolefin and n is an integer greater than 1 which comprises reacting a polymerizablc compound containing a double bond between two carbon atoms and two fluorine atoms attached to at least one of the carbon atoms at a temperature between about 0 C. and about 200 C. for a period of time between about one-half hour and about 24 hours under liquid phase and substantially anhydrous conditions in the presence of a catalyst effective under the conditions of reaction to promote the reaction in the presence of sulfuryl chloride in a mol ratio between about 1 to 10 and about 2 to l with the monomer such that sulfuryl chloride provides chlorine terminal groups and sulfur dioxide is released, to produce a. distillable open chain compound and recovering the compound thus produced.

10. The process of claim 9 in which said polymerizable compound is trifluorochloroethylene.

11. The process of claim 9 in which said polymerizable compound is tetrafluoroethylene.

12. The process of claim 9 in which said polymerizable compound is unsym. diohlorodifiuoroethylene.

13. A process for the production of a distillable open chain compound having the general formula in which X and Y are different haloolefins and n and m are integers at least one of which is greater than 1 which comprises reacting a polymerizable compound containing a double bond between two carbon atoms and two fluorine atoms attached to at least one of the carbon atoms and another haloethylenic compound at a temperature between about C. and about 200 C. for a period of time between about onehalf hour and about 24 hours under liquid phase and substantially anhydrous conditions in the presence of a catalyst efiective under the conditions of reaction to promote the reaction in the presence of sulfuryl chloride in a mol ratio between about 1 to 10 and about 2 to 1 with the monomer such that the sulfuryl chloride provides chlorine terminal groups and sulfur dioxide is released.

14. The process of claim 13 in which trifluorochloroethylene is reacted with tetrafiuoroethylene.

15. A process for the production of a distillable open chain compound having the general formula in which n is an integer greater than 1 which comprises reacting chlorotrifiuoroethylene at a temperature between about C. and about 125 C. for a period of time between about 2 hours and 5 hours under liquid phase and anhydrous conditions in the presence of benzoyl peroxide and sulfuryl chloride such that the sulfuryl chloride provides chlorine terminal groups and sulfur dioxide is released, said sulfuryl chloride being in a mol ratio between about 1 to 1 and about 1 to 4 with the monomer.

16. A composition of the formula Cl(CF2CF2)nCl having a boiling range between C. and 300 C.

17. A composition of the formula Cl(OF2CF2)1 Cl having a melting point of about 80 C.

18. A mixture of compounds boiling between 200 C. and 550 C. having the formula Cl(CF2CFCl)-C1.

19. A mixture of compounds boiling between 350 and 450 C. having the formula Cl(CF2CFCl)nC1.

20. A mixture of compounds melting at 96 C. having the formula Cl(CFgCFCl)-nCl.

References Cited in the file of this patent UNITED STATES PATENTS 2,411,159 Hanford Nov. 19, 1946 2,440,800 Hanford et al May 4, 1948 2,562,547 Hanford et al. July 31, 1951 

1. A PROCESS FOR THE PRODUCTION OF A DISTILLABLE OPEN CHAIN COMPOUND HAVING A GENERAL FORMULA SELECTED FROM THE GROUP CONSISTING OF
 18. A MIXTURE OF COMPOUNDS BOILING BETWEEN 200* C. AND 550* C. HAVING THE FORMULA C1-(CF2CFC1)N-C1. 